Spherical Aberration-corrected Electron Microscopy Research Articles

Efficient and Robust Hydrogen Evolution: Phosphorus Nitride Imide Nanotubes as Supports for Anchoring Single Ruthenium Sites

Amorphous phosphorus nitride imide nanotubes (HPN) are reported as a novel substrate to stabilize materials containing single-metal sites. Abundant dangling unsaturated P vacancies play a role in stabilization. Ruthenium single atoms (SAs) are successfully anchored by strong coordination interactions between the d orbitals of Ru and the lone pair electrons of N located in the HPN matrix. The atomic dispersion of Ru atoms can be distinguished by X-ray absorption fine structure measurements and spherical aberration correction electron microscopy. Importantly, Ru SAs@PN is an excellent electrocatalyst for the hydrogen evolution reaction (HER) in 0.5 m H2 SO4 , delivering a low overpotential of 24 mV at 10 mA cm-2 and a Tafel slope of 38 mV dec-1 . The catalyst exhibits robust stability in a constant current test at a large current density of 162 mA cm-2 for more than 24 hours, and is operative for 5000 cycles in a cyclic voltammetry test. Additionally, Ru SAs@PN presents a turnover frequency (TOF) of 1.67 H2 s-1 at 25 mV, and 4.29 H2 s-1 at 50 mV, in 0.5 m H2 SO4 solution, outperforming most of the reported hydrogen evolution catalysts. Density functional theory (DFT) calculations further demonstrate that the Gibbs free energy of adsorbed H* over the Ru SAs on PN is much closer to zero compared with the Ru/C and Ru SAs supported on carbon and C3 N4 , thus considerably facilitating the overall HER performance.

Efficient and Robust Hydrogen Evolution: Phosphorus Nitride Imide Nanotubes as Supports for Anchoring Single Ruthenium Sites

AbstractAmorphous phosphorus nitride imide nanotubes (HPN) are reported as a novel substrate to stabilize materials containing single‐metal sites. Abundant dangling unsaturated P vacancies play a role in stabilization. Ruthenium single atoms (SAs) are successfully anchored by strong coordination interactions between the d orbitals of Ru and the lone pair electrons of N located in the HPN matrix. The atomic dispersion of Ru atoms can be distinguished by X‐ray absorption fine structure measurements and spherical aberration correction electron microscopy. Importantly, Ru SAs@PN is an excellent electrocatalyst for the hydrogen evolution reaction (HER) in 0.5 m H2SO4, delivering a low overpotential of 24 mV at 10 mA cm−2 and a Tafel slope of 38 mV dec−1. The catalyst exhibits robust stability in a constant current test at a large current density of 162 mA cm−2 for more than 24 hours, and is operative for 5000 cycles in a cyclic voltammetry test. Additionally, Ru SAs@PN presents a turnover frequency (TOF) of 1.67 H2 s−1 at 25 mV, and 4.29 H2 s−1 at 50 mV, in 0.5 m H2SO4 solution, outperforming most of the reported hydrogen evolution catalysts. Density functional theory (DFT) calculations further demonstrate that the Gibbs free energy of adsorbed H* over the Ru SAs on PN is much closer to zero compared with the Ru/C and Ru SAs supported on carbon and C3N4, thus considerably facilitating the overall HER performance.

Single-Site AuI Catalyst for Silane Oxidation with Water.

Single-site Au anchored on mpg-C3 N4 (519 ppm Au loading) is developed as a highly active, selective, and stable catalyst for the oxidation of silanes with water with a turnover frequency as high as 50 200 h-1 , far exceeding most known catalysts based on total gold content. Other hydrosilanes bearing unsaturated functional groups also lead to corresponding silanols under mild reaction conditions without formation of any side products in good or excellent yields. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Au atoms stabilized by mpg-C3 N4 . The coordination of the catalytically active AuI by three nitrogen or carbon atoms in the tri-s-triazine repeating units not only prevents the Au atoms from aggregation, but also renders the surface AuI highly active, which is completely different than homogeneous AuI species.

Uncoordinated Amine Groups of Metal-Organic Frameworks to Anchor Single Ru Sites as Chemoselective Catalysts toward the Hydrogenation of Quinoline.

Here we report a precise control of isolated single ruthenium site supported on nitrogen-doped porous carbon (Ru SAs/N-C) through a coordination-assisted strategy. This synthesis is based on the utilization of strong coordination between Ru3+ and the free amine groups (-NH2) at the skeleton of a metal-organic framework, which plays a critical role to access the atomically isolated dispersion of Ru sites. Without the assistance of the amino groups, the Ru precursor is prone to aggregation during the pyrolysis process, resulting in the formation of Ru clusters. The atomic dispersion of Ru on N-doped carbon can be verified by the spherical aberration correction electron microscopy and X-ray absorption fine structure measurements. Most importantly, this single Ru sites with single-mind N coordination can serve as a semihomogeneous catalyst to catalyze effectively chemoselective hydrogenation of functionalized quinolones.

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials.

Single Cobalt Atoms with Precise N‐Coordination as Superior Oxygen Reduction Reaction Catalysts

AbstractA new strategy for achieving stable Co single atoms (SAs) on nitrogen‐doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal–organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X‐ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as‐generated N‐doped porous carbon. Surprisingly, the obtained Co‐Nx single sites exhibit superior ORR performance with a half‐wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non‐precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials.

Phason space analysis and structure modelling of 100 Å-scale dodecagonal quasicrystal in Mn-based alloy

The dodecagonal quasicrystal classified into the five-dimensional space group P126/mmc, recently discovered in a Mn–Cr–Ni–Si alloy, has been analysed using atomic-resolution spherical aberration-corrected electron microscopy, i.e. high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and conventional transmission electron microscopy. By observing along the 12-fold axis, non-periodic tiling consisting of an equilateral triangle and a square has been revealed, of which common edge length is a = 4.560 Å. These tiles tend to form a network of dodecagons of which size is a ≈ 17 Å in diameter. The tiling was interpreted as an aggregate of 100 Å-scale oriented domains of high- and low-quality quasicrystals with small crystallites appearing at their boundaries. The quasicrystal domains exhibited a densely filled circular acceptance region in the phason space. This is the first observation of the acceptance region in an actual dodecagonal quasicrystal. Atomic structure model consistent with the electron microscopy images is a standard Frank-Kasper decoration of the triangle and square tiles that can be inferred from the crystal structures of Zr4Al3 and Cr3Si. Four kinds of layers located at z = 0, ±1/4 and 1/2 are stacked periodically along the 12-fold axis, and the atoms at z = 0 and 1/2 form hexagonal anti-prisms consistently with the 126-screw axis. The validity of this structure model was examined by means of powder X-ray diffraction.

Ti-substituted tunnel-type Na₀.₄₄MnO₂ oxide as a negative electrode for aqueous sodium-ion batteries.

The aqueous sodium-ion battery system is a safe and low-cost solution for large-scale energy storage, because of the abundance of sodium and inexpensive aqueous electrolytes. Although several positive electrode materials, for example, Na₀.₄₄MnO₂, were proposed, few negative electrode materials, for example, activated carbon and NaTi₂(PO₄)₃, are available. Here we show that Ti-substituted Na₀.₄₄MnO₂ (Na₀.₄₄[Mn₁-xTix]O₂) with tunnel structure can be used as a negative electrode material for aqueous sodium-ion batteries. This material exhibits superior cyclability even without the special treatment of oxygen removal from the aqueous solution. Atomic-scale characterizations based on spherical aberration-corrected electron microscopy and ab initio calculations are utilized to accurately identify the Ti substitution sites and sodium storage mechanism. Ti substitution tunes the charge ordering property and reaction pathway, significantly smoothing the discharge/charge profiles and lowering the storage voltage. Both the fundamental understanding and practical demonstrations suggest that Na₀.₄₄[Mn₁-xTix]O₂ is a promising negative electrode material for aqueous sodium-ion batteries.

Reversible contrast in focus series of annular bright field images of a crystalline LiMn2O4 nanowire

A through-focus series of annular bright field (ABF) images were observed simultaneously with high-angle annular dark field (HAADF) images of very thin lithium manganese oxide (LiMn₂O₄), a typical cathode material used in lithium ion batteries, using a spherical aberration corrected electron microscope with a 50 pm resolution (R005). The ABF images showed dark dips at the positions of Li and Mn--O atomic columns, which reversed to bright peaks when the defocus sign was changed, as commonly observed in phase contrast images. The optimal defocus for the ABF images was about 2 nm of over-focus, while that for the HAADF images was 2 nm of under-focus for an incident probe with a convergent semi-angle of 30 mrad. These experimental results are interpreted based on a weak-phase-object approximation.

Chromatic Confocal Electron Microscopy with a Finite Pinhole Size

Scanning confocal electron microscopy (SCEM) is a new imaging mode in electron microscopy. Spherical aberration corrected electron microscope instruments fitted with two aberration correctors can be used in this mode which provides improved depth resolution and selectivity compared to optical sectioning in a conventional scanning transmission geometry. In this article, we consider the depth resolution and energy resolution in the confocal optical configuration for SCEM using inelastically scattered electrons with a finite pinhole size. We experimentally demonstrate energy-filtered optical sectioning in a double aberration-corrected instrument with uncorrected chromatic aberration without using a dedicated energy filter.

球面収差補正透過型電子顕微鏡法を用いたアトミックスケールでの構造解析

球面収差補正透過型電子顕微鏡法を用いたアトミックスケールでの構造解析

Visualization of Lithium Atoms using Ultra High-Resolution TEM

Distribution of lithium ions in crystals is an important issue for development of advanced lithium ion batteries. Using spherical aberration-corrected electron microscope, lithium columns in crystals have been visualized with heavy element ones by a new method of scanning transmission electron microscopy (STEM) called as annular bright field (ABF) imaging. ABF images are taken by setting an annular detector in bright field disk. It is so powerful that it visualizes not only lithium but also hydrogen columns in battery and storage materials. Some suggested explanations of ABF imaging mechanism, hollow-cone beam illumination method, phase object approximation and s-state channeling model, will be reviewed.

Counting lithium ions in the diffusion channel of an LiV2O4 crystal

As a new microscopic method to reveal lithium ion behavior in lithium ion batteries, we demonstrated that lithium atoms in the diffusion channel of the spinel structure (LiV2O4 crystal) were visualized and their number was countable one-by-one by using annular bright field imaging method in conjunction with a spherical aberration corrected electron microscope: the lithium column intensity varied by a step of single lithium atom in correlation with the thickness change of the LiV2O4 crystal, in accordance with theoretical image simulations.

Experimental setup for energy-filtered scanning confocal electron microscopy (EFSCEM) in a double aberration-corrected transmission electron microscope

Scanning confocal electron microscopy (SCEM) is a new imaging mode in electron microscopy. Spherical aberration corrected electron microscope instruments fitted with two aberration correctors can be used in this mode which provides improved depth resolution and selectivity compared to optical sectioning in a conventional scanning transmission geometry. In this article, we consider a confocal optical configuration for SCEM using inelastically scattered electrons. We lay out the necessary steps for achieving this new operational mode in a double aberration-corrected instrument with uncorrected chromatic aberration and present preliminary experimental results in such mode.

Visualization of Lithium Atoms in LiV2O4 by a Spherical Aberration Corrected Electron Microscope

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Direct imaging of lithium atoms in LiV2O4 by spherical aberration-corrected electron microscopy

We visualized lithium atom columns in LiV₂O₄ crystals by combining scanning transmission electron microscopy with annular bright field (ABF) imaging using a spherical aberration-corrected electron microscope (R005) viewed from the [110] direction. The incident electron beam was coherent with a convergent angle of 30 mrad (semi-angle), and the detector collected scattered electrons over 20-30 mrad (semi-angle). The ABF image showed dark dots corresponding to lithium, vanadium and oxygen columns.

STEM imaging of 47-pm-separated atomic columns by a spherical aberration-corrected electron microscope with a 300-kV cold field emission gun

A spherical aberration-corrected electron microscope has been developed recently, which is equipped with a 300-kV cold field emission gun and an objective lens of a small chromatic aberration coefficient. A dumbbell image of 47 pm spacing, corresponding to a pair of atomic columns of germanium aligned along the [114] direction, is resolved in high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) with a 0.4-eV energy spread of the electron beam. The observed image was compared with a simulated image obtained by dynamical calculation.